WO1991002017A1 - Copolymere de dodecane terephtalamide - Google Patents

Copolymere de dodecane terephtalamide Download PDF

Info

Publication number
WO1991002017A1
WO1991002017A1 PCT/US1990/003030 US9003030W WO9102017A1 WO 1991002017 A1 WO1991002017 A1 WO 1991002017A1 US 9003030 W US9003030 W US 9003030W WO 9102017 A1 WO9102017 A1 WO 9102017A1
Authority
WO
WIPO (PCT)
Prior art keywords
copolymer
diacid
additional comonomer
percent
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1990/003030
Other languages
English (en)
Inventor
Murali Krishna Akkapeddi
Jeffrey Harper Glans
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell International Inc
Original Assignee
AlliedSignal Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by AlliedSignal Inc filed Critical AlliedSignal Inc
Priority to EP90910198A priority Critical patent/EP0485396B1/fr
Priority to DE69021385T priority patent/DE69021385T2/de
Publication of WO1991002017A1 publication Critical patent/WO1991002017A1/fr
Priority to KR1019920700206A priority patent/KR0171611B1/ko
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids

Definitions

  • the present invention is in the field of polyamides, more particularly, the present invention relates to copolymers derived from long chain diamines, a symmetrical diacid or derivative thereof, and at least one specifically selected additional comonomer.
  • nylons such as polycaprolactam (nylon 6), poly(hexamethylene adipamide) (nylon 6)
  • Long chain aliphatic polyamides such as polylaurolactam (nylon 12), and poly(1,12-dodecamethylenedodecanamide) (nylon 12,12) have low moisture-absorbing properties, but have undesirably low itelting points (below 180oC).
  • Symmetrical rigid, aromatic diacids such as terephthalic acid monomers used with aliphatic diamines having from 6 to 12 carbon atoms result in polyamides having low moisture absorbing characteristics but undesirably high melting points (greater than 300oC). Such melting points are often above the nylon degradation temperatures so that the polyamide cannot be melt-polymerized or melt-processed.
  • the present invention is an improved polyamide copolymer derived from a long chain diamine, preferably
  • RHN[CH 2 ] n NHR where n is from 10 to 14, and preferably is
  • R is preferably H or an alkyl carbonyl group such as resulting in the
  • the diacid is a symmetrical aromatic dicarboxylic acid.
  • the symmetrical aromatic diacid or derivative thereof is preferably selected from the group consisting of terephthalic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-biphenyl
  • the copolymer has minor amounts, preferably 3 to 30 and more preferably 5 to 10 mol percent, of an additional component
  • Useful and preferred additional comonomers include units derived from monomers which are difunctional.
  • the functional groups are groups which are reactive with the amine groups of the diamine or the acid groups of the diacid.
  • Preferred functional groups include amine groups, hydroxyl groups and carboxylic acid groups.
  • Specific andpreferred comonomers include lactams having up to 9 methylene groups, nonsymmetrical aromatic diacids, and hydroxy terminated polyolefins or polyethers.
  • the resulting polyamide copolymer will have high crystallinity and low moisture absorption, or the additional comonomer will contribute a "soft segment" making the polyamide copolymer more flexible.
  • Additional comonomers which result in the improved crystallinity and low moisture absorption of the polyamide copolymer are preferably present in an amountsufficient to reduce the melting point while at the same time enable the polymer to have high crystallinity and low moisture absorption properties.
  • the additional comonomer results in a polyamide copolymer havingrelatively high crystalline melting points of preferably from 250oC to 300oC, and more preferably 270oC to 290oC, high crystallinity, preferably at least 20 percent, and low moisture absorption, preferably below 5 percent, and more preferably below 3 weight percent based on the weight of polyamide eopolymer and moisture.
  • the additional comonomer can be preferably present in random or block segments thereby resulting in a random or block copolymer.
  • the major blocks of polyamide are derived from the long chain diamine and the symmetrical diacid.
  • Preferred additional comonomers include diamines and nonsymmetrical diacids.
  • Preferred diamines include 4,9-dioxa-dodecane--1,12-diamine; 4,11-dioxa-tetradecane-1,14-diamine; caprolactam, and laurolactam.
  • Preferred nonsymmetrical diacids include phthalic acid and isophthalic acid.
  • Comonomers which result in a polyamide copolymer having a flexible (low glass transition temperature, Tg), hydrophobic structure include block segments of polyolefin polyether and polysiloxane and the like. Preferred segments include telechelic amine terminated polyolefins including polyethylene, poly(ethylene-propylene), polyiso- butylene, poly(ethylene-butene), and the like. Preferred polyether, is bisamino alkyl, polytetramethyleneoxide (derived from polytetrahydrafuran), and preferred
  • polysiloxane is poly(dimethyl siloxane); i.e., alpha,- omega-bisaminoalkyl poly(dimethyl siloxane). These comonomers have been found to act as a "soft segment" when used in the form of a block copolymer. The resulting copolymer has a combination of properties including high ductility (tensile-elongation), heat and chemical
  • the present invention is a polyamide copolymer comprising units derived from a long chain diamine
  • RHN[CH 2 ] n NHR where n is from 10 to 14 and preferably is 12 (i.e., 1,12-dodecanediamine); and R is preferably H or an alkyl carbonyl group such as C
  • symmetrical diacid and derivatives thereof preferably a symmetrical aromatic diacid and derivatives thereof, preferably where Ar is an aromatic group
  • R 1 is preferably -OH, alkoxy group such as -OCH 3 , or a halogen resulting in the monomer repeat unit
  • Useful Ar's include
  • the symmetrical aromatic diacid is preferably selected from the group consisting of terephthalic acid, 2,6-naphthalene dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid and dimethyl terephthalate.
  • the preferred polyamide copolymer has units derived from 1,12-dodecanediamine copolymerized with a terephthalic acid and the additional comonomer.
  • the copolymer comprises from 35 to 48.5 mol
  • the copolymer comprises at least 3, and preferably from 3 to 30, and more preferably from 5 to 10 mol percent of units derived from the additional comonomer.
  • copolymer having a relatively high melting point, high crystallinity, and has low moisture absorption
  • the preferred polyamide copolymer has a melting point below a copolymer derived from a
  • the melting point of the preferred polyamide copolymer is preferably in the range of from 250oC to 300oC, and more preferably 270oC to 290oC.
  • the polyamide copolymer is highly crystalline asmeasured by X-ray diffraction.
  • the polyamide copolymer is preferably at least 20 percent, and more preferably at least 30 percent.
  • the upper range of crystallinity is typically 40 percent mol and preferably 50 percent crystalline.
  • the polyamide copolymer has low moisture absorption characteristics as measured according to ASTM D 570-81.
  • the polyamide copolymer absorbs less than 5 percent by weight, and preferably less than 3 percent by weight of moisture based on the weight of the polyamide copolymer and moisture.
  • Preferred additional comonomers which lead to co-crystallizable segments, or at least do not significantly reduce crystallinity are diamines such as 4,9-dioxa-1,12-diaminododecane; 4, 11-dioxa-tetradecane-1,14-diamine;
  • non-symmetrical diacids including isophthalic acid
  • lactams having up to 8 methylene groups preferably laurolactam and caprolactam.
  • Copolyamides made using these additional comonomers have been found to have crystalline melting points of from 270-285oC, a low water absorption character of 1.7-3 percent by weight when measured according to ASTM D 570-81, good melt
  • copolyamides have been found to have excellent chemical resistance, particularly to aqueous zinc chloridesolutions.
  • the polyamide copolymers have been found to be dimensionally stable when exposed to heat and moisture, and have chemical resistance to gasoline and alcohol as well as a variety of other organic materials. This makes the copolymers of the present invention useful for a variety of high-performance engineering resin applications, such as automotive under-the-hood parts, fuel lines, and fuel component parts.
  • An alternate embodiment of the polyamide copolymer can include comonomer units to improve flexibility of the copolymer.
  • Comonomers having a flexible hydrophobic structure resulting in a soft segment include the olefins present as polyolefin segments such as polyethylene, poly(ethylene-propylene), polyisobutylene, poly(ethylene- butene), and the like.
  • a preferred ether is a polyether such as bis [aminopropyl]polytetrahydrafuran (derived from polytetramethyleneoxide); alpha,omega-bis(aminoalkyl)-poly(tetramethyleneoxide); alpha,omega-diamino
  • polyolefins i.e., telechelic, amino terminated
  • polyethylene and polysiloxanes such as poly(dimethyl siloxane); i.e., alpha,omega-bisaminoalkyl poly(dimethyl siloxane).
  • the molecular weight of the soft segments preferably range from 200 to 6,000 and more preferably from 750 to 2100.
  • Polyethylene oxide is not preferred because of the high water absorption.
  • the additional comonomer preferably is derived f rom comonomers resulting in units having the formula
  • R 2 is selected from -H, -CH 3 , -C 2 H 5 , -Cl,
  • R 3 is selected from -H, -CH 3 , -C 2 H 5 , -CH-CH 2 , and mixtures thereof,
  • A is selected from H, a halogen, and a hydrocarbon having from 1 to 4 carbon atoms,
  • p is from 5 to 80
  • q is from 10 to 80, r is from 1 to 30, preferably 5 to 30,
  • s is from 4 to 9
  • x is from 4 to 6
  • ⁇ ' is from 2 to 6.
  • the copolymer of the present invention can be made by conventional methods to copolymerize polyamides. Particularly preferred are melt polymerization techniques in which the monomers are melted together under an inert atmosphere.
  • the melt polymerization preferably is
  • polymerizable monomers can also be used to prepare copolymers. Included in these are vinyl compounds and other monomers which could be polymerized directly into a linear polymer chain.
  • the quantity of such additional monomers can vary and can be up to 30 mol percent of the total number of polymerizable constituents but preferably is limited to quantities of less than 15 mol percent, more preferably less than 5 mol percent.
  • copolymerizations of 1,2-dodecanediamine, terephthalic acid and the indicated additional comonomer were performed in the indicated equipment with mechanical stirring under a sweep of an inert gas (either nitrogen or argon). In each case the polymerizations were run until a significant increase in viscosity was noted and then the sample was allowed to cool. The resulting solid was broken up and ground in a Wiley® mill to produce a powder.
  • Reduced viscosities were determined by samples dissolved in m-cresol or concentrated sulfuric acid.
  • Samples to be tested in accordance with ASTM tests were injection molded using an Arburg® injection molding machine at 320oC and 450 psi conditions. Tensile tests were performed on molded samples according to ASTM D-638 procedures. Water absorption measurements were performed on thin compression-molded films according to ASTM-D-570-81. Films were compression-molded at 300oC for 1 minute at 10 to 20 tons of pressure. The films were 0.1 mm thick. The films were submerged in water and their change in weight monitored until equilibrium.
  • Zinc chloride resistance was measured by immersing a bent 1/8 inch test bar in a 50 wt. percent solution of zinc chloride.
  • the test bars were molded as described above, 7 inches long by 3/4 inch at the tabs, 1/4 inch in the neck region and 1/8 inch thick (ASTM-D-638 test bars).
  • a 500 ml stainless steel resin kettle with a mechanical stirrer was charged with 51.1 g (0.255 mol) of 1,12-dodecanediamine, 5.79 g (0.28 mol) of 4,9-dioxadodecane-1,12-diamine, 44.9 (0.270 mol) of terephthalic acid, and 50 ml of water.
  • the polymerization mixture was slowly heated to 320°C to give a clear viscous melt. The polymer was allowed to cool and broken up. The resulting resin was dried overnight at 110oC under vacuum.
  • a three liter glass resin kettle was charged with 517.1 g (2.58 mol) of 1,12-dodecanediamine, 226.9 g (0.30 mol) of bisaminopropoxypolytetrahydrofuran 750, 456.0 g (2.74 mol) of terephthalic acid, and 400 ml of water.
  • the mixture was siowly heated to 293oC to give a viscous melt.
  • the melt was allowed to cool to room temperature, ground up, and dried overnight at 100oC under vacuum. This sample was unaffected by immersion in a zinc chloride solution for over one month.
  • a one liter stainless steel resin kettle fitted with a mechanical stirrer and an argon sweep was charged with 286.1 g (1.43 mol) of 1,12-dodecanediamine, 203.6 g (1.23 mol) of terephthalic acid, 22.6 g (0.14 mol) of isophthalic acid, and 400 ml of water.
  • the kettle was slowly heated to 300oC under a sweep of argon.
  • the resulting polymer was broken up, and dried (110oC, vacuum) overnight.
  • Example 6 A 0.5 L stainless steel kettle was charged with 6.8 g (60.0 mmol) of caprolactam, 113.6 g (567 mmol) of
  • 1,12-dodecanediamine 1,12-dodecanediamine, 89.7 g (540 mmol) of terephthalic acid and 200 ml of water.
  • the reaction mixture was slowly heated to 300oC which resulted in a viscous melt.
  • the resulting material was allowed to cool, broken up, and dried overnight at 110oC under vacuum.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyamides (AREA)

Abstract

Copolymère de polyamide amélioré comprenant des unités de monomères comportant des unités de répétition de la formule (I), dans laquelle n est compris entre 10 et 14 et représente de préférence 12 (1,12-dodécanediamine), des unités dérivées d'un diacide symmétrique ou d'un dérivé de ce dernier, de préférence d'un acide dicarboxylique aromatique symétrique. Ledit copolymère comporte de faibles quantités, de préférence 3 à 30 et idéalement de 5 à 10 moles pourcent d'unités dérivées d'un comonomère additionnel.
PCT/US1990/003030 1989-07-31 1990-05-31 Copolymere de dodecane terephtalamide Ceased WO1991002017A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP90910198A EP0485396B1 (fr) 1989-07-31 1990-05-31 Copolymère de dodécane téréphthalamide
DE69021385T DE69021385T2 (de) 1989-07-31 1990-05-31 Copolymer aus dodecan-terephthalamid.
KR1019920700206A KR0171611B1 (ko) 1989-07-31 1992-01-29 도데칸 테레프탈아미드의 공중합체

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US38818289A 1989-07-31 1989-07-31
US388,182 1989-07-31

Publications (1)

Publication Number Publication Date
WO1991002017A1 true WO1991002017A1 (fr) 1991-02-21

Family

ID=23533026

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1990/003030 Ceased WO1991002017A1 (fr) 1989-07-31 1990-05-31 Copolymere de dodecane terephtalamide

Country Status (6)

Country Link
EP (1) EP0485396B1 (fr)
JP (1) JP2509759B2 (fr)
KR (1) KR0171611B1 (fr)
CA (1) CA2064093A1 (fr)
DE (1) DE69021385T2 (fr)
WO (1) WO1991002017A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0678526A3 (fr) * 1990-06-08 1997-01-15 Tonen Corp Polymères d'éthylène ayant les deux extrémités modifiées et leurs procédés de préparation.

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015101675A (ja) * 2013-11-26 2015-06-04 チェイル インダストリーズ インコーポレイテッド ポリアミド成形体およびその製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2116379A1 (fr) * 1970-10-20 1972-07-13 Standard Oil Co
US3790423A (en) * 1971-11-22 1974-02-05 Phillips Petroleum Co Method of bonding using a polyamide resin
US3843611A (en) * 1972-05-22 1974-10-22 Phillips Petroleum Co Copolyamide from terephthalic acid,dodecanedioic acid and dodecane diamine

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58154723A (ja) * 1982-03-09 1983-09-14 Daicel Chem Ind Ltd 新規共重合ポリアミド樹脂の製造方法
JP2557348B2 (ja) * 1985-09-18 1996-11-27 三井石油化学工業 株式会社 成形材料用ポリアミドおよび成形材料用ポリアミド組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2116379A1 (fr) * 1970-10-20 1972-07-13 Standard Oil Co
US3790423A (en) * 1971-11-22 1974-02-05 Phillips Petroleum Co Method of bonding using a polyamide resin
US3843611A (en) * 1972-05-22 1974-10-22 Phillips Petroleum Co Copolyamide from terephthalic acid,dodecanedioic acid and dodecane diamine

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACT, Volume 78, No. 8, 26 February 1973, (Columbus, Ohio, US), see page 64, Abstract 44934x, & JP, A, 7229451 (Toray Industries, Inc.) 2 August 1972 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0678526A3 (fr) * 1990-06-08 1997-01-15 Tonen Corp Polymères d'éthylène ayant les deux extrémités modifiées et leurs procédés de préparation.
EP0530408B1 (fr) * 1990-06-08 1997-02-19 Tonen Corporation Polymères d'oléfine ayant les deux extrémités modifiées et leurs procédés de préparation

Also Published As

Publication number Publication date
JPH04507427A (ja) 1992-12-24
JP2509759B2 (ja) 1996-06-26
KR0171611B1 (ko) 1999-05-01
DE69021385D1 (de) 1995-09-07
KR927003686A (ko) 1992-12-18
EP0485396A1 (fr) 1992-05-20
CA2064093A1 (fr) 1991-02-01
EP0485396B1 (fr) 1995-08-02
DE69021385T2 (de) 1996-02-29

Similar Documents

Publication Publication Date Title
KR0168468B1 (ko) 폴리아미드 및 폴리아미드 조성물
CA1195041A (fr) Melanges de polyamides
US5391640A (en) Miscible thermoplastic polymeric blend compositions containing polyamide/amorphous polyamide blends
AU658954B2 (en) New polyamides and objects obtained from them
US4387184A (en) Heat stable polyphase polyamide compositions and preparation thereof
CN101374884B (zh) 半结晶半芳族聚酰胺
KR940011164B1 (ko) 신규한 코폴리아미드와 그의 제조방법
US4404317A (en) Polyamide blends
KR20020092840A (ko) 폴리아미드 조성물
CA1167996A (fr) Polyamides
CN1233693C (zh) 基于四亚甲基对苯二酰胺和六亚甲基对苯二酰胺的共聚酰胺
JPH04227633A (ja) 混合アミンからポリエーテルアミドを製造する方法
US4346024A (en) Heat-stable polyphase polyamide/polyesteramide compositions
JPH04227632A (ja) 新規なポリエーテルアミド及びその製法
US4556697A (en) Alternating copolyamide prepared on a polymer matrix
CN113150269A (zh) 半芳香族聚酰胺共聚物及其制备
US4555566A (en) Copolymer polyamide resin containing polyolefin moiety
US5399663A (en) Poly(etheramide) segmented block copolymers
JPH04227634A (ja) テトラエチレングリコールジアミン及び芳香族ジカルボン酸からのポリエーテルアミドの製法
CA1181191A (fr) Melange renfermant des polyamides thermoplastiques, semi-cristallises et amorphes, ainsi qu'un agent de durcissement a base de polymere organique
US5079339A (en) Copolymer of dodecane terephthalamide
JPS642131B2 (fr)
EP0485396B1 (fr) Copolymère de dodécane téréphthalamide
EP0035551B1 (fr) Copolymere en bloc de polyetheramide et copolymere isotrope de polyamide et de polyetheramide
KR20140086770A (ko) 폴리아미드 수지, 이의 제조방법 및 이를 포함하는 성형품

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA JP KR

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB IT LU NL SE

WWE Wipo information: entry into national phase

Ref document number: 1990910198

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2064093

Country of ref document: CA

WWP Wipo information: published in national office

Ref document number: 1990910198

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 1990910198

Country of ref document: EP